Photoluminescent and electroluminescent studies of bilayer heterojunctions formed from a poly(pyridyl vinylene phenylene vinylene) (PPyVPV) derivative and poly(vinyl carbazole) (PVK) show an emission peak which cannot be ascribed to either the PPyVPV derivative or PVK layer. Through studies of absorption and photoluminescence excitation (PLE) spectra we demonstrate that the additional feature results from an exciplex at the bilayer interface. The photoluminescence efficiency of the exciplex is greater than 20&percent;. The electroluminescence spectrum from the bilayer devices is entirely due to exciplex emission, with internal efficiencies initially achieved exceeding 0.1&percent;. ©1997 American Institute of Physics.